CN109096113B - Method for aromatizing synthetic oak moss - Google Patents
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- CN109096113B CN109096113B CN201811067935.6A CN201811067935A CN109096113B CN 109096113 B CN109096113 B CN 109096113B CN 201811067935 A CN201811067935 A CN 201811067935A CN 109096113 B CN109096113 B CN 109096113B
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- dimethyl
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- aromatizing
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- 238000000034 method Methods 0.000 title claims abstract description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 230000020477 pH reduction Effects 0.000 claims description 11
- -1 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl chloride Chemical compound 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- DLSXDJHNHAKETI-UHFFFAOYSA-N methyl 3,6-dimethyl-2,4-dioxocyclohexane-1-carboxylate Chemical class COC(=O)C1C(C)CC(=O)C(C)C1=O DLSXDJHNHAKETI-UHFFFAOYSA-N 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- 238000006845 Michael addition reaction Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000003512 Claisen condensation reaction Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for aromatizing synthetic oak moss, which comprises the steps of adding chlorinated 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate into acetonitrile serving as a solvent for aromatization reaction, and then cooling and crystallizing to obtain a synthetic oak moss crude product. Compared with the prior art, the method for aromatizing the synthetic oak moss has the following advantages: 1. the by-product sodium chloride generated by the reaction can be directly filtered out; 2. the water of reaction can be recycled; 3. during aromatization reaction, the reaction is not violent because the aromatization reaction is carried out in acetonitrile solvent, and the generated hydrogen chloride is easy to recover; 4. the post-treatment process is simple, and the purity of the produced crude product is up to more than 98%. Therefore, the method provides an improved process method for synthesizing the oak moss, which is environment-friendly, energy-saving and capable of realizing industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to an improved method for aromatizing synthetic spice, in particular to a method for aromatizing synthetic oak moss.
Background
The oak moss has unique oak moss-like fragrance and good fragrance-fixing agent, and is widely applied to perfumed soaps, detergents, high-grade perfumes and tobaccos. In the past, natural oak moss extract is used, and the oak moss extract is discolored by alkali and is difficult to prepare soap essence. The synthetic oak moss has no such disadvantages.
The present synthesis method of oak moss is reported in West German patent publication 2, 359, 233(1974) that dimethyl malonate is used as raw material, and condensed in methanol solution of sodium methoxide to obtain dihydro oak moss intermediate, which is then aromatized by using reagents such as N-bromocaprolactone amine, etc. and its reaction time is long and cost is high. West German patent publication 2,653,177 (1978) aromatizes waste acid with inexpensive reagents such as acetic anhydride, concentrated sulfuric acid, etc.
International flavor and essence company patent CN106631794A A preparation method of oak moss crystal flavor adopts one-pot synthesis method to synthesize oak moss crystal, the method uses methanol as solvent and water, the produced salt water has bad color, and methanol is used for aromatization to produce methyl chloride, because the boiling point of methyl chloride is only-22 deg.C, it is not suitable for recovery.
Disclosure of Invention
In view of the above, the present invention aims to provide a new method for improving the aromatization of synthetic oak moss to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the method comprises the steps of adding chlorinated 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate into acetonitrile serving as a solvent for aromatization reaction, and then cooling and crystallizing to obtain a crude product of the synthesized oak moss.
Further, the aromatization reaction is carried out under the condition of 60-90 ℃ for 4-20 hours, wherein the weight ratio of the 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl chloride to the acetonitrile is 1 (1-5).
Further, the preparation method of the chlorinated 3, 6-dimethyl-2, 4-dioxo-cyclohexanecarboxylic acid methyl ester comprises the following steps: (1) 4-hexene-3-ketone and dimethyl malonate are subjected to Michael addition reaction and intramolecular claisen condensation reaction under the condition of sodium methoxide, and then acid acidification and suction filtration are carried out to obtain 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate;
(2) adding 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl formate into water and chloralkane, and introducing chlorine gas to carry out chlorination reaction.
Further, in the step (2), the weight ratio of the 3, 6-dimethyl-2, 4-dioxo-cyclohexanecarboxylic acid methyl ester to the water is 1: (1-5).
Further, in the step (2), the weight ratio of the 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl formate to the chloralkane is 1: (1-5), wherein the chloroalkane is dichloromethane, chloroform or carbon tetrachloride.
Further, the acidification process in the step (1) is to adopt hydrochloric acid with the mass fraction of 30%, and the saturated saline solution obtained after acidification is filtered and recycled.
Further, hydrogen chloride generated in the aromatization process is absorbed by water and then is used in an acidification process in the preparation method of the 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate.
Further, hydrogen chloride generated in the aromatization process is absorbed by three stages of water, wherein one stage is saturated absorption and is used for an acidification procedure in the preparation method of the 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate.
Compared with the prior art, the method for aromatizing the synthetic oak moss has the following advantages:
1. the by-product sodium chloride generated by the reaction can be directly filtered out; 2. the water of reaction can be recycled; 3. during aromatization reaction, the reaction is not violent because the aromatization reaction is carried out in acetonitrile solvent, and the generated hydrogen chloride is easy to recover; 4. the post-treatment process is simple, and the purity of the produced crude product is up to more than 98%. Therefore, the method provides an improved process method for synthesizing the oak moss, which is environment-friendly, energy-saving and capable of realizing industrial production.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The technical scheme of the invention is that 2, 5-dimethyl-dihydro-beta-methyl-fulminate is separated in water and chloralkane, chlorine is introduced for chlorination reaction, reaction liquid is separated after the chlorination reaction is finished, saturated saline water is filtered for recycling, and filtered sodium chloride is sold as a byproduct. After the reaction liquid is recovered by the solvent, acetonitrile is added as the solvent, aromatization reaction is carried out at the temperature of 55-90 ℃, and the generated hydrogen chloride is absorbed and then acidified for recycling. After the reaction is finished, the crude oak moss product with the content of more than 98 percent is obtained by suction filtration, and the acetonitrile is recycled.
Wherein, the raw material 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl formate is solid obtained by carrying out Michael addition acidification on dimethyl malonate and 4-hexene-3-ketone. The specific chemical reaction formula is as follows:
the present invention will be described in detail with reference to examples.
Example 1
Putting 200g of 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl formate, 400g of water and 400g of dichloromethane into a 2000ml four-mouth bottle, introducing 800g of chlorine gas at 0-25 ℃, separating an organic phase, collecting the dichloromethane in the organic phase, adding 300g of acetonitrile, aging at 80 ℃ for 5 hours, recovering 200g of acetonitrile, cooling and suction-filtering to obtain a crude product of oak moss, drying a filter cake to obtain 113g of a product with the purity of 98.2% and the yield of 90.9%.
Example 2
200g of methyl 3, 6-dimethyl-2, 4-dioxo-cyclohexanecarboxylate (containing sodium chloride neutralized by Michael addition reaction), 400g of dichloromethane and water separated in example 1 were put into a 2000ml four-necked flask, 800g of chlorine gas was introduced at 0 to 25 ℃, then the organic phase was separated, dichloromethane in the organic phase was collected, 600g of acetonitrile was added, reaction was carried out at 85 ℃ for 10 hours, 450g of acetonitrile was recovered, crude synthetic oak moss was obtained by cooling and suction filtration, and the crude synthetic oak moss was dried to obtain 112.5g of a product with a purity of 98.1% and a yield of 90.5%.
Example 3
200g of methyl 3, 6-dimethyl-2, 4-dioxo-cyclohexanecarboxylate (containing sodium chloride neutralized by Michael addition reaction), 600g of dichloromethane and water separated in example 2 are added into a 2000ml four-necked flask, 800g of chlorine gas is introduced at 0-25 ℃, then an organic phase is separated, sodium chloride is filtered from an aqueous phase to completely recover dichloromethane in the organic phase, 900g of acetonitrile is added for reacting for 18 hours at 86 ℃, 790g of acetonitrile is recovered, the temperature is reduced to 10 ℃, then crude oak moss is obtained by suction filtration, and 110g of a product with the purity of 98.6 percent and the yield of 88.5 percent is obtained after drying.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A method for aromatizing synthetic oak moss is characterized by comprising the following steps: adding chlorinated 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate into acetonitrile serving as a solvent for aromatization reaction, and then cooling and crystallizing to obtain a synthesized oak moss crude product;
the chlorinated 3, 6-dimethyl-2, 4-dioxo-cyclohexanecarboxylic acid methyl ester has the formula:
2. a process for the aromatization of synthetic oak moss according to claim 1 wherein: the aromatization reaction is carried out under the condition of 60-90 ℃ for 4-20 hours, wherein the weight ratio of the 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl chloride to the acetonitrile is 1 (1-5).
3. A process for aromatizing synthetic oak moss according to claim 1 or 2 wherein: the preparation method of the chlorinated 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate comprises the following steps: (1) 4-hexene-3-ketone and dimethyl malonate are subjected to Michael addition reaction and intramolecular claisen condensation reaction under the condition of sodium methoxide, and then acid acidification and suction filtration are carried out to obtain 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate;
(2) adding 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl formate into water and chloralkane, and introducing chlorine gas to carry out chlorination reaction.
4. A process of aromatizing synthetic oak moss according to claim 3 wherein: in the step (2), the weight ratio of the 3, 6-dimethyl-2, 4-dioxo-cyclohexanecarboxylic acid methyl ester to the water is 1: (1-5).
5. A process for aromatizing synthetic oak moss according to claim 3 wherein: in the step (2), the weight ratio of the 3, 6-dimethyl-2, 4-dioxo-cyclohexane methyl formate to the chloralkane is 1: (1-5), wherein the chloroalkane is dichloromethane, chloroform or carbon tetrachloride.
6. A process of aromatizing synthetic oak moss according to claim 3 wherein: the acidification process in the step (1) is to adopt hydrochloric acid with the mass fraction of 30%, and the saturated salt water obtained after acidification is recycled after filtration.
7. A process of aromatizing synthetic oak moss according to claim 3 wherein: the hydrogen chloride generated in the aromatization process is absorbed by water and then is used in the acidification procedure of the preparation method of the 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate.
8. A process for aromatizing synthetic oak moss according to claim 7 wherein: the hydrogen chloride generated in the aromatization process is absorbed by three stages of water, wherein the first stage is saturated absorption and is used for the acidification procedure in the preparation method of the 3, 6-dimethyl-2, 4-dioxo-methyl cyclohexanecarboxylate.
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| CN201811067935.6A CN109096113B (en) | 2018-09-13 | 2018-09-13 | Method for aromatizing synthetic oak moss |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811067935.6A CN109096113B (en) | 2018-09-13 | 2018-09-13 | Method for aromatizing synthetic oak moss |
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| CN109096113A CN109096113A (en) | 2018-12-28 |
| CN109096113B true CN109096113B (en) | 2021-05-25 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3634491A (en) * | 1968-08-30 | 1972-01-11 | Int Flavors & Fragrances Inc | Process for the preparation of 3 5-dialkyl resorcylic acids and esters |
| US3884843A (en) * | 1974-01-31 | 1975-05-20 | Fritzsche Dodge & Olcott Inc | Alkyl monomethyl-ringsubstituted-diacetoxy-benzoate perfume compositions |
| CN86100869A (en) * | 1986-01-10 | 1987-07-22 | 中国科学院上海有机化学研究所 | The chemosynthesis of the main essence of oak moss |
| CN102351706A (en) * | 2011-08-04 | 2012-02-15 | 江苏中烟工业有限责任公司 | Method for synthesizing ethyldivaricatinate and application of ethyldivaricatinate |
| CN106631794A (en) * | 2016-09-28 | 2017-05-10 | 国际香料和香精公司 | Process for preparing perfume 2,5-dimethylmethyl resorcylate |
-
2018
- 2018-09-13 CN CN201811067935.6A patent/CN109096113B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3634491A (en) * | 1968-08-30 | 1972-01-11 | Int Flavors & Fragrances Inc | Process for the preparation of 3 5-dialkyl resorcylic acids and esters |
| US3884843A (en) * | 1974-01-31 | 1975-05-20 | Fritzsche Dodge & Olcott Inc | Alkyl monomethyl-ringsubstituted-diacetoxy-benzoate perfume compositions |
| CN86100869A (en) * | 1986-01-10 | 1987-07-22 | 中国科学院上海有机化学研究所 | The chemosynthesis of the main essence of oak moss |
| CN102351706A (en) * | 2011-08-04 | 2012-02-15 | 江苏中烟工业有限责任公司 | Method for synthesizing ethyldivaricatinate and application of ethyldivaricatinate |
| CN106631794A (en) * | 2016-09-28 | 2017-05-10 | 国际香料和香精公司 | Process for preparing perfume 2,5-dimethylmethyl resorcylate |
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| CN109096113A (en) | 2018-12-28 |
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